New Catalytic Systems

This part surveys the development of new solid acid catalysts such as metal oxides, including nanosheets, nanotubes, mesoporous materials, carbon-based catalysts, and ion-exchanged resins. Recent achievements in carbon-carbon bond formation, one-pot sequential reactions by sobd acids and bases, and acid-base bifunctional catalysts are also included. 

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From a historical perspective it is interesting to note that the Nozaki experiment was, in fact, a mechanistic probe to establish the intermediacy of a copper carbe-noid complex rather than an attempt to make enantiopure compounds for synthetic purposes. To achieve synthetically useful selectivities would require an extensive exploration of metals, ligands and reaction conditions along with a deeper understanding of the reaction mechanism. Modern methods for asymmetric cyclopropanation now encompass the use of countless metal complexes [2], but for the most part, the importance of diazoacetates as the carbenoid precursors still dominates the design of new catalytic systems. Highly effective catalysts developed in... 

An expedient and stereoselective synthesis of bicyclic ketone 30 exemplifies the utility and elegance of Corey s new catalytic system (see Scheme 8). Reaction of the (R)-tryptophan-derived oxazaboro-lidine 42 (5 mol %), 5-(benzyloxymethyl)-l,3-cyclopentadiene 26, and 2-bromoacrolein (43) at -78 °C in methylene chloride gives, after eight hours, diastereomeric adducts 44 in a yield of 83 % (95 5 exo.endo diastereoselectivity 96 4 enantioselectivity for the exo isomer). After reaction, the /V-tosyltryptophan can be recovered for reuse. The basic premise is that oxazaborolidine 42 induces the Diels-Alder reaction between intermediates 26 and 43 to proceed through a transition state geometry that maximizes attractive donor-acceptor interactions. Coordination of the dienophile at the face of boron that is cis to the 3-indolylmethyl substituent is thus favored.19d f Treatment of the 95 5 mixture of exo/endo diastereo-mers with 5 mol % aqueous AgNC>3 selectively converts the minor, but more reactive, endo aldehyde diastereomer into water-soluble... 

This review deals with the chemistry and coordination complexes of isoelectronic analogues of common oxo-anions of phosphorus such as PO3, POl", RPOl" and R2POy. The article begins with a discussion of homoleptic systems in which all of the 0x0 ligands are replaced by imido (NR) groups. This is followed by an account of heteroleptic phosphorus-centered anions, including [RN(E)P(/<-NR )2P(E)NR]2-, [EP(NR)3]3-, [RP(E)(NR)2] and [R2P(E)(NR )] (E=0,S, Se, Te). The emphasis is on the wide variety of coordination modes exhibited by these poly-dentate ligands, which have both hard (NR) and soft (S, Se or Te) centers. Possible applications of their metal complexes include new catalytic systems, coordination polymers with unique properties, and novel porous materials. 

Horlbeck, G., Siesler, H. W., Tittle, B., and Trafara, G., Characterization of polyether and polyester homo- and copolymers prepared by ring-opening poljnnerization with a new catalytic system. Macromolecules. 10. 284-287, 1977. 

The attainment of regio- and enantioselectivity are continuing challenges, which form the basis of investigations of new catalytic systems. For example, novel mixed-metal catalysts such as (CO)2Co(u-CO)(u-HC=CBu)Rh(CO)2 promote the stereospecific synthesis of Z-only BuC (CHO) = CHSiMe2Ph from 1-hexyne and HSiMe2Ph.1364... 

We shall deal in this lecture with recent improvements in the elastomers synthesis, that should be able to cope with the above mentioned requirements, without resorting to important investments for new plants or to cumbersome feedstocks. The improvement of the elastomer synthesis relies upon new catalytic systems that allow a control of elastomer tacticity in order to achieve a strain induced crystallization, and suitable monomer combinations in order to minimize the hysteresis loss of the elastomer in a wide range of temperatures and frequencies. 

This chapter illustrates that synthetic reactions via C-H bond activation became popular in the past 10 years and are noted as one of the active fields in organic synthesis. The development of new catalytic systems will improve the selectivity and the scope of the reactions, and open up new reactions. 

Since the discovery by Ziegler and Natta that transition metal complexes, in the presence of aluminum alkyl compounds, can efficiently catalyze the polymerization of ethylene and propylene, significant efforts have been devoted to the development of new catalytic systems for polymerization of olefins. One of the... 

Carbonylation of unsaturated substrates has been known for decades but the reaction selectivity has been progressively improved by tuning the coordination sphere of late transition metal-based catalysts. Palladium assumes a privileged place in this chemistry and its versatility allows the use of mild conditions for the selective incorporation of CO into acyclic and cyclic compounds. Further improvements open a path to more sophisticated reactions, particularly cascade reactions. Similarly, asymmetric versions of most of these carbonylations can be envisioned. Atom economy and the green character of the process will probably be the key criteria for evaluating any new catalytic system. 

Thus, if the incorporation of some metal oxides indicated a notable improvement in the catalytic activity (permitting it to operate at lower reaction temperatures),the incorporation of metals, especially Pt and working in the presence of H2, has prolonged the hfe of the catalysts. However, new catalyst formulations have recently increased the resistance of these catalysts to such poisons as water or sulfur during the isomerization of n-C5 and n-C6 paraffins. Nevertheless, the use of other anions, by supporting WO3 or MoOf or heteropolyacids,which have higher thermal stability, can also be interesting alternative routes to develop new catalytic systems. 

It is about 20 years since the combination of transition-metal catalysis and electroreduction was shown to be applicable to the coupling of organic molecules. This was followed by a number of fundamental investigations and basic syntheses using various nickel, cobalt, or pdladium compounds which can easily be reduced in situ electrochemically to low-valent reactive intermediates. The last decade has been less characterized by reports on new catalytic systems than by the development of new synthetic applications. The aim of this review is to show that the electrochemical processes described here offer valuable advantages in organic synthesis. 

The last two decades have witnessed great strides in the contribution of catalysis to the advancement of petrochemistry and related fields. New catalytic systems and catalysts added much to the discovery and improvement of catalytic processes as a result of a better understanding of catalytic reactions and the availability of new analytical tools. 

The hydrocarboxylation of styrene (Scheme 5.12) and styrene derivatives results in the formation of arylpropionic acids. Members of the a-arylpropionic acid family are potent non-steroidal anti-inflammatory dmgs (Ibuprofen, Naproxen etc.), therefore a direct and simple route to such compounds is of considerable industrial interest. In fact, there are several patents describing the production of a-arylpropionic acids by hydroxycarbonylation [51,53] (several more listed in [52]). The carbonylation of styrene itself serves as a useful test reaction in order to learn the properties of new catalytic systems, such as activity, selectivity to acids, regioselectivity (1/b ratio) and enantioselectivity (e.e.) in the branched product. In aqueous or in aqueous/organic biphasic systems complexes of palladium were studied exclusively, and the results are summarized in Table 5.2. 

In an earlier report, Maitlis et al. showed that 1 could be easily converted into a hydrido complex [Cp lrHCl]2 (2) under ambient conditions by treatment with alcohol and a weak base (Scheme 5.1) [19], probably accompanied by the formation of carbonyl compounds. This fact means that the hydrogen atom in an alcohol can be rapidly transferred to the iridium center in the form of a hydride but then, if the hydride on the iridium could be re-transferred to another hydrogen acceptor, a new catalytic system using alcohols as substrates might be realized. In fact, a wide variety of Cp Ir complex-catalyzed hydrogen transfer systems using alcohols as substrates, and based on the above hypothesis, have been reported to date [20]. 

Interestingly, fundamentally different stereoinduction mechanisms have been proposed for the activation of a number of related imine substrates, studies that resulted in the development of simple and highly effective new catalytic systems (27) for the addition of silyl ketene acetals to Al-Boc-protected aldimines (Mannich reaction) (Scheme 11.12c). ... 

Titanium in the framework of pentasil zeolites induces oxygenation activity with diluted hydrogen peroxide as oxidant, thus constituting a new catalytic system. 

On the whole, all proposed mechanisms contain three relevant steps (1) coordination of the olefin and oxygen, (2) C - O bond formation, (3) elimination of the ketone with regeneration of the catalytically active species. In recent years, rather than searching for new catalytic systems based on rhodiiun and iridium compounds, attention has been focused on understanding the organometallic chemistry involved in the oxygenation of C = C bonds, as described in Sect. 3. 

Recent study on sulfonium ylide [2,3]-sigmatropic rearrangement has been focused on the development of new catalytic systems, including new catalysts and alternative carbene precursor other than commonly used a-diazocarbonyl compounds. Besides the most commonly used Cu(i) and Rh(ii) catalysts, Fe com-... 

Besides aU achievements in the area of transition-metal catalysis, there is a need for finding new catalytic systems which meet the requirements of high efficiency, low... 

In 2007, Cahiez and coworkers disclosed two new catalytic systems to improve the reaction, especially for large-scale syntheses. In the first catalytic system, iron(III) acetylacetonate is used instead of iron(III) chloride. In addition, the use of hexamethylenetetramine (HMTA, 5%), a very cheap new ligand, allows one to significantly lower the amount of TMEDA (10% instead of 120%) (Scheme 42). This catalytic system is based on a synergy between TMEDA and HMTA. 

Ruthenium(II) complexes bearing atropisomeric diphosphine ligands have proved to be efficient systems for the hydrogenation of a wide range of prochiral substrates. A new catalytic system has been developed based on ruthenium complexes having SYNPHOS and DIFLUORPHOS as chiral diphosphanes (Figure 3.6). 

The oxidation of sulfides to sulfones has been the subject of extensive studies, since sulfones are useful synthons for the construction of various chemically and biologically significant moleculesJ Recently, a new catalytic system has been developed by exchanging potassium osmate onto chloride-saturated layered double hydroxides (Figure 9.1), which we have shown to be an efficient catalyst for the direct oxidation of sulfides to sulfones, using molecular oxygen as the stoichiometric oxidant and with delivery of two oxygen atoms simultaneously to the sulfide, reminiscent of olefin dihydroxylation reactions. 

This led us to find new catalytic systems able to turn the electrochemical process to the synthesis of organozinc compounds. In this context, a simple cobalt halides salt can be used advantageously6. As a matter of fact, the work devoted to the study of the... 

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